(ZrM)-(CuN)-Ni-Al-RE amorphous alloy and manufacturing method and application thereof

ABSTRACT

The present invention relates to a (ZrM)-(CuN)—Ni—Al-RE amorphous alloy, which containing, by atom percent, 40-65% of Zr, 18-46% of Cu, 2-15% of Ni, 4-15% of Al, 0.1-3% of M, 0.05-3% of N, 0.1-2% of a rare earth element RE, wherein M is Hf and/or Ti; and N is Ag, wherein the amorphous alloy further contains a small amount of Hf, Ti, Ag and Re on the basis of a Zr—Al—Ni—Cu amorphous alloy, to maintain the mechanical properties of the Zr—Al—Ni—Cu amorphous alloy, and has a relatively strong glass froming ability, manufacturability and antimicrobial property.

FIELD OF INVENTION

The present invention relates to a Zr-based amorphous alloy preparationtechnology, and more particularly to a (ZrM)-(CuN)—Ni—Al-RE amorphousalloy having a high glass froming ability and preparation andapplication thereof.

DESCRIPTION OF RELATED ARTS

Zr-based amorphous alloys have many excellent properties due to theirstructural specificities, such as high strength (1500-2000 MPa), highhardness (about HRC 50), high elasticity limit (about 2%), excellentcorrosion resistance and liquid near-net formability, etc., they haveimportant application prospects in the fields of consumer electronics,medical and health, aerospace and transportation and other fields.

For the Zr-based amorphous alloy, a variety of alloy compositions havebeen developed, such as the Zr—Ti—Cu—Ni—Be system alloy developed in theUnited States, having a critical cooling rate of 1K/s, and with a strongglass froming ability and a high manufacturability. However, theapplication range of the alloy system is limited by its toxicBe element.Zr—Ti—Cu—Ni—Al and Zr—Nb—Cu—Ni—Al amorphous alloy have an amorphous sizeof φ15 mm and a relatively weak glass froming ability. Japan developed aZr—Al—Ni—Cu alloy system, has an amorphous size of φ30 mm. However, thealloy system requires more strict preparation conditions, high-purityraw materials and high vacuum preparation technology, which restrict itsapplication.

In order to improve the glass froming ability of the Zr-based amorphousalloy, a large amount of research work has been done by adjusting thecompositions of the Zr—Cu—Ni—Al alloy and adding alloying elements,which mainly focused on the forming ability of the Zr—Cu—Ni—Al amorphousalloy itself. Ag, Ti, Fe, Hf and rare earth RE elements are addedseparately to the Zr—Cu—Ni—Al alloy, or Ag and Re are addedsimultaneously, but the principle of addition is not clearly stated (oris not clear), so that the added element and its content is nottargeted, and the amorphous manufacturability of the alloy is notsignificantly improved or unknown.

The manufacturability (ie, the manufacturability of the amorphous alloyby employing industrial grade raw materials, low vacuum preparation andmultiple cyclic utilization) of the Zr—Cu—Ni—Al alloy in the applicationprocess determines its application feasibility. Aiming at this, thepresent invention has developed a (ZrM)-(CuN)—Ni—Al-(RE) amorphous alloyhaving excellent glass froming ability and manufacturability, excellentmechanical properties and more excellent antibacterial andbacteriostatic function, have broad application prospects in theconsumer electronics, health care, transportation and other fields.

SUMMARY OF THE PRESENT INVENTION

The present invention provides a Zr—Cu—Ni—Al alloy having thecomposition of M, N and RE elements, wherein the (ZrM)-(CuN)—Ni—Al-(RE)alloy has a high glass froming ability and manufacturability, excellentmechanical properties and antibacterial and bacteriostatic functions,which laid the application foundation of the alloy.

The conventional Zr—Cu—Ni—Al amorphous alloy has excellent mechanicalproperties and forming ability, but its manufacturing ability isrelatively poor, that is, in the practical application of thepreparation process, the forming, defect control, production efficiencyand cost and other factors have to be considered together: the purity ofraw materials and the preparation vacuum are relatively low, whichresult in its decreased glass froming ability, decreasedmanufacturability and limited practical application.

The present invention comprehensively considers the glass fromingability and manufacturability of Zr—Cu—Ni—Al type amorphous alloy, andaims to solve the bottleneck problem that restricts its application. Itis found that the Zr—Cu—Ni—Al alloy can easily precipitate CuZr compoundduring the solidification process. If the precipitation of CuZr compoundis effectively inhibited, the manufacturability of Zr—Cu—Ni—Al can beimproved.

In the present invention, a small amount of Cu-like and Zr-like and rareearth RE elements are added: Cu-like element: N (Ag), Zr-like element M(Hf, Ti), so during the precipitate process, Cu and N elements competewith each other to form the compounds (CuZr and AgCu compounds) with Zrelement, and Zr and M (Hf, Ti) elements compete with each other to formthe compounds (such as CuZr, CuHf). The result of competing with eachother is that the solidification process is complicated, theprecipitation of CuZr is inhibited, and the glass froming ability andmanufacturability of Zr—Cu—Ni—Al are improved.

The addition of rare earth element RE can effectively reduce the effectof the increase of the oxygen content on the glass froming ability dueto the low degree of vacuum. On the one hand, the rare earth element REis combined with oxygen to form oxide, floating on its surface, thusinhibiting the combination of oxygen and other elements, on the otherhand, the addition of RE increases the complexity of alloying elements,to enhance the glass froming ability thereof. The simultaneous additionof M, N and RE in the Zr—Cu—Ni—Al alloy significantly increases theforming ability and manufacturability of the alloy. Adding separately M,N or RE have a certain role, but simultaneously adding these elementswill generate a best result.

The technical solution of the present invention is as follows:

A (ZrM)-(CuN)—Ni—Al-RE amorphous alloy for manufacturing a mechanicalcomponent, which containing:

40-65% of Zr, 18-46% of Cu, 2-15% of Ni, 4-15% of Al, 0.1-3% of M,0.05-3% of N, 0.1-2% of a rare earth element RE, wherein M is Hf and/orTi, and N is Ag, the rare earth element RE is Y, Gd, Er, Sc or acombination thereof.

The preferably composition ratio: Zr: 50˜55%, Cu: 28˜35%, Ni: 4˜7%, Al:5˜11%, M: 0.1˜1.0%, N: 0.05˜1.0%, rare earth element RE: 0.1˜1.0%.

The present invention is characterized in that a small amount of M, Nand RE elements are simultaneously added into the basis alloy ofZr—Cu—Ni—Al. In practical applications, the factors such as cost,mechanical properties and surface quality of samples are taken intoaccount. The atomic percentages of Hf, Ag and RE elements are controlledat 1%, and the atomic percentage of Ti is controlled at ≦2%.

The method for preparing (ZrM)-(CuN)—Ni—Al-RE amorphous alloy accordingto the present invention, is characterized in that, preparing a motheralloy ingot by an arc melting process or an induction melting process,by using Zr, Cu, Ni, Al, M, N and RE as raw materials; heating themother alloy ingot by arc heating or induction heating process; and thenpreparing the amorphous alloy by casting or die casting process, whereinthe process parameter is: vacuum degree is 1×10¹˜10⁻³, or being filledwith argon, the melting temperature is 860˜1200° C., and the coolingrate is 10˜10³ K/s.

The (ZrM)-(CuN)—Ni—Al-RE amorphous alloy of the present invention can beused in the fields of consumer electronics, medical and health,aerospace or transportation, for manufacturing complex components.

The (ZrM)-(CuN)—Ni—Al-RE amorphous alloy described in the presentinvention has the following characteristics:

1, The amorphous alloy has a high forming ability, in particular, has agood manufacturability, and its optimal glass froming ability is greaterthan 20 mm. Utilizing industrial manufacturing technology, the alloyrepeated melting-casting preparation samples more than 4 times, stillable to form amorphous, so as to ensure the quality and meet the actualproduction needs.

2, The mechanical properties of the amorphous alloy are as follows: thecompressive fracture strength is greater than 1500 Pa, and the amorphousalloy has a more excellent antibacterial and bacteriostatic function,for the presence of Ag element is in the alloy.

3, The preparation raw materials can be industrial grade of metal Zr,Cu, Ni, Al, M, N and RE, and the vacuum is not demanding.

4, The amorphous alloy can be widely used in consumer electronics,health care, transportation and other fields, and is an ideal materialfor manufacturing complex, thin-walled parts, which has a broadapplication prospect.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of an amorphous alloy component.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

All raw materials (Zr, Hf, Ti, Cu, Ni, Al, Ag, Y, Gd, Sc) used in thisembodiment are industrial grade metals, Zr and Ti metals are spongezirconium, sponge titanium, Hf can be sponge zirconium containing acertain amount of Hf, which are prepared according to the atomicpercentage. And then, prepare the mother alloy ingot by arc melting orinduction melting, under the protection of argon. In order to ensure theuniform of the refined alloy ingot, the refined alloy ingot need to beflipped 3 to 4 times during the arc melting process of the mother alloyingot, and then obtaining the mother alloy ingot by Cu mold casting andinduction heating, wherein the heating temperature is about 1000° C.,the vacuum is 10⁻¹˜10⁻² Pa.

Examples 1 to 23 shown in Table 1 (the same preparation process):

TABLE 1 Composition of (ZrM)—(CuN)—Ni—Al—RE alloy, amorphous size andmechanical properties Amorphous Strength NO Alloy Composition (%) size(mm) (Mpa) 1 Zr_(50.4)Hf_(0.4)Cu_(35.9)Ag_(0.1)Ni₄Al₉Y_(0.2) ≧8 1830 2Zr_(50.4)Hf_(0.4)Cu_(35.9)Ag_(0.1)Ni₄Al₉Gd_(0.2) ≧5 1620 3Zr_(51.6)Hf_(0.4)Cu_(34.9)Ag_(0.1)Ni₅Al_(7.5)Y_(0.5) ≧8 1800 4Zr_(51.6)Hf_(0.4)Cu_(34.9)Ag_(0.1)Ni₅Al_(7.5)Gd_(0.5) ≧6 1630 5Zr₅₀Ti₂Cu_(34.9)Ag_(0.1)Ni₅Al_(7.5)Y_(0.5) ≧6 1820 6Zr₅₀Ti₂Cu_(34.9)Ag_(0.1)Ni₅Al_(7.5)Gd_(0.5) ≧6 1650 7(Zr_(51.8)Hf_(0.4)Cu₃₅Ag_(0.1)Ni₆Al_(6.7))₉₈Y₂ ≧8 1780 8(Zr_(54.6)Hf_(0.4)Cu_(29.9)Ag_(0.1)Ni₅Al₁₀)₉₈Y₂ ≧12 1800 9(Zr_(63.9)Hf_(0.5)Cu₁₈Ag_(0.1)Ni₁₀Al_(7.5))₉₈Y₂ ≧5 1780 10(Zr_(54.6)Hf_(0.4)Cu_(29.9)Ag_(0.1)Ni₅Al₁₀)_(99.5)Y_(0.5) ≧15 1820 11(Zr_(54.4)Hf_(0.4)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀)_(99.5)Y_(0.5) ≧20 1800 12(Zr_(49.96)Hf_(0.5)Cu_(35.19)Ni_(2.65)Ag_(2.15)Al_(9.55))_(99.5)Y_(0.5)≧12 1812 13(Zr_(49.72)Hf_(0.4)Cu_(35.22)Ni_(2.69)Ag_(2.69)Al_(9.28))_(99.5)Y_(0.5)≧20 1810 14(Zr_(49.40)Hf_(0.4)Cu_(35.20)Ni_(2.73)Ag_(3.24)Al_(9.03))_(99.5)Y_(0.5)≧20 1810 15 (Zr_(50.1)Hf_(0.4)Cu_(31.5)Ni₄Al₁₁Ag₃)_(99.5)Y_(0.5) ≧201890 16 (Zr_(48.2)Hf_(0.3)Cu₃₆Ag_(0.5)Ni₄Al₉Ti₂)_(99.5)Y_(0.5) ≧12 179017 Zr₅₅Cu₃₀Ni₅Al₁₀   4 mm 1750 18 Zr₅₄Ti₁Cu₃₀Ni₅Al₁₀ 4.5 mm 1760 19Zr₅₄Hf₁Cu₃₀Ni₅Al₁₀ 4.5 mm 1770 20 Zr₅₅Cu_(29.9)Ag_(0.1)Ni₅Al₁₀   5 mm1740 21 Zr_(54.4)Hf_(0.4)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀   8 mm 1790 22(Zr_(54.8)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀)_(99.5)Y_(0.5)  15 mm 1800 23(Zr_(48.2)Hf_(0.3)Cu_(36.5)Ni₄Al₉Ti₂)_(99.5)Y_(0.5) ≧10 1785

The antimicrobial properties of the amorphous alloy can be measured by acoating method (see JIS Z 2801-2000) to detect its sterilization rateagainst common Escherichia coli ATCC25922, wherein the concentration ofbacteria is 4.2×10⁵ cfu/ml. The results show that the bactericidal rateof the amorphous alloy against Escherichia coli is more than 99.9%.

Example 24

By utilizing (Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10)99.5Y0.5 alloy to prepareamorphous components by vacuum die casting method, under the conditionsof induction melting 30 kg alloy, vacuum 10⁻¹˜10⁻² Pa and heatingtemperature 900˜1000° C. After repeating 5 times, the prepared componentcan still guarantee the amorphous structure of the alloy material. Theprepared component is shown in FIG. 1. After Re-use 4 times, the alloycasted φ5 mm sample can still guarantee the formation of amorphous.

Comparative Example 1

The Zr55Cu30Ni5Al10 alloy is one of the Zr—Cu—Ni—Al quaternary amorphousalloys having strongest forming capacity, reported in the literature,and its forming capacity is φ30 mm. However, the alloy system requires avery demanding on the purity of the composition and preparationconditions. when employing industrial materials, under vacuum of1×10¹˜10⁻² Pa, its amorphous size is merely φ4 mm; when addingseparately a small amount of Hf or Ti element, the amorphous size of theZr₅₄Hf₁Cu₃₀Ni₅Al₁₀ (Zr₅₄Ti₁Cu₃₀Ni₅Al₁₀) is merely φ4.5 mm; when addingseparately a small amount of Ag element, the amorphous size of theZr₅₅Cu_(29.9)Ag_(0.3)Ni₅Al₁₀ is φ5 mm; when adding simultaneously asmall amount of Hf and Ag elements, the amorphous size of theZr_(54.4)Hf_(0.4)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀ is φ8 mm; when addingsimultaneously a small amount of Ag and Y elements, the amorphous sizeof the (Zr_(54.8)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀)_(99.5)Y_(0.5) is φ15 mm; andwhen adding simultaneously a small amount of Hf, Ag and Y elements, theamorphous size of the(Zr_(54.4)Hf_(0.4)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀)_(99.5)Y_(0.5) is more thanφ20 mm.

Comparative Example 2

Preparing the sample of Zr_(54.4)Hf_(0.4)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀amorphous alloy the second time, which has been crystallized partly,however, the sample of(Zr_(54.4)Hf_(0.4)Cu_(29.9)Ag_(0.3)Ni₅Al₁₀)_(99.5)Y_(0.5) amorphousalloy repeats 4 times, which is still amorphous, and the sample is φ5×50mm round bar.

1. A (ZrM)-(CuN)—Ni—Al-(RE) amorphous alloy adapted for preparing amechanical component, comprising: by atomic percent, 40-65% of Zr,18-46% of Cu, 2-15% of Ni, 4-15% of Al, 0.1-3% of M, 0.05-3% of N,0.1-2% of a rare earth element RE, wherein M is Hf and/or Ti, and N isAg, the rare earth element RE is Y, Gd, Er, Sc or a combination thereof.2. The (ZrM)-(CuN)—Ni—Al-(RE) amorphous alloy according to claim 1,wherein by atomic percent, the percentages of Hf, Ag and RE are no morethan 1% respectively, and the percentage of Ti is no more than 2%. 3.The (ZrM)-(CuN)—Ni—Al-RE amorphous alloy according to claim 1, whereinby atomic percent, the amorphous alloy is optimized to comprise: 50-55%of Zr, 28-35% of Cu, 4-7% of Ni, 5-11% of Al, 0.1-1.0% of M, 0.05-1.0%of N, 0.1-1.0% of a rare earth element RE.
 4. A manufacturing method forthe (ZrM)-(CuN)—Ni—Al-RE amorphous alloy according to claim 1,comprising the following steps: preparing a master ingot by an arcmelting process or an induction melting process, by using Zr, Cu, Ni,Al, M, N and RE as raw materials; preparing the amorphous alloy bycasting or die casting process, after melting master ingot by archeating or induction heating technique, wherein the process parameteris: vacuum degree is 1×10¹˜10⁻³ Pa, or being filled with argon, themelting temperature is 860˜1200° C., and the cooling rate is 10˜10³ K/s.5. An application of the (ZrM)-(CuN)—Ni—Al-RE amorphous alloy accordingto claim 1, the amorphous alloy is capable of being can be used in thefields of electronics, medical and health, aerospace or traffictransport.
 6. The application of the (ZrM)-(CuN)—Ni—Al-RE amorphousalloy, recited in claim 5, wherein the amorphous alloy is capable ofbeing used for making can make complex components.